Polysiloxane cosmetic composition

ABSTRACT

A hair-treating and skin-treating composition comprising a liquid preferably aqueous dispersion containing a mixture of two type of polysiloxanes, one being amino- and hydroxy- or alkoxy-functional, the other being carboxy- or carboxyl-ester-functional containing at least two carboxyl groups, the composition being characterized by ready removability from hair and skin after drying by washing.

This invention relates to a composition comprising a novel liquiddispersion containing a combination of two types of siloxane polymersand a method of making the same. The composition is useful either aloneor in combination with additional components as a cosmetic compositionfor treating hair or for application to skin.

There have previously been proposed in U.S. Pat. Nos. 4,409,267,4,419,391, and 4,631,207, a variety of amino-functional polysiloxanesfor treating fabrics or fibers or for waterproofing masonry. In Huhn etal. U.S. Pat. No. 4,559,385, there were described complex mixtures ofhydroxy-functional polysiloxanes, amino-functional polysiloxanes, organosilanes, and a condensation catalyst for treating a variety of naturaland synthetic fibers. Hair treating compositions containing aminofunctional polysiloxanes have been described in Cornwall et al. U.S.Pat. No. 4,586,518, Fridd et al, U.S. Pat. No. 4,601,902, and Traver etal. U.S. Pat. No. 4,618,689. in Sebag et al. U.S. Pat. No. 4,342,742 andSebag et al. U.S. Pat. No. 4,490,536, there were described polysiloxaneproducts having ay one of a variety of hydrophilic groups includingamino-functional and carboxy-functional groups bonded to the siliconatoms by a decamethylene chain. The products were said to be useful in avariety of hair treating compositions including shampoos, dyes, settinglotions and waving compositions.

In Japanese Pat. No. 58605 (1982) there was described a compositioncontaining an amino functional polysiloxane along with a dibasiccarboxylic acid or an amino acid for use in cosmetics applied to hairand skin. In Japanese Pat. No. 144179 (1983) there was described aprocess for treating cloth to make it durably water repellent byapplying to it in sequence an amino functional polyalkoxysilane,followed by carboxy- or carboxy ester-functional polysiloxane. Ona etal. U.S. Pat. No. 4,311,626 described a composition for treating naturalor synthetic fibers and fabrics to impart a combination of propertiesdurable to washing and dry cleaning; the composition contained an aminofjunctional polysiloxane free from alkoxy and hydroxy groups, and acarboxy functional polysiloxane. Nakano et al. U.S. Pat. No. 4,658,049described a carboxy-functional polysiloxane having a variety of uses,and published European Patent Application No. 0095238 described theapplication to hair of a composition comprising (1) a polysiloxanecontaining a functional group that provides attachment to the hair, (2)a surfactant (3) a freeze-thaw stablizer and (4) water. Grollier et al.U.S. Pat. No. 4,240,450 described compositions for treating hair or skincomprising a combination of a cationic polymer with an anionic polymer,the polymers being conventional carbon-type polymers free from siliconor siloxane groups.

It has now been found that a composition comprising a liquid, preferablyaqueous, dispersion of two different types of polysiloxanes possessesunique advantages for treating fibers and particularly for treating hairor skin, as in a cosmetic composition. The composition when applied tohair or skin solidifies or "dries" rapidly within a few minutes afterapplication at a temperature of 20°-30° C. and is then characterized bythe fact that it can be essentially completely removed by washing withan aqueous solution of surface active agent, such as a shampoo or soapsolution. Despite this ready removability, however, the dried film ofthe composition surprisingly remains highly resistant to moisture and toremoval by water alone, and serves to retain the curl and set of thehair for an extended period even when exposed to conditions of highhumidity and subjected to repeated combing; when applied to skin itserves to retain moisture. Other agents conventionally present in hairor skin treating compositions may optionally be added to provide a hairconditioner, insect repellent lotion or cream, sunscreen, or skinmoisturizer, for example. The dispersion, with or without optionaladditives, when applied to hair, provides not only set retention butalso high sheen, desirable tactile properties, and ease of combing, thusserving as a set holding cream rinse.

The composition of the present invention includes as one of the twotypes of polysiloxanes, a carboxy- or carboxyl- ester-functionalpolysiloxane (type I) having the following composition: ##STR1## inwhich R is a monovalent hydrocarbon group having 1 to 20 carbon atoms,preferably an alkyl or benzyl group having 1 to 7 carbon atoms,

R' is hydrogen or a monovalent hydrocarbon group such as an alkyl group,preferably hydrogen.

Q is a divalent hydrocarbon group having 1 to 8 carbon atoms, preferablyan alkylene group having 1 to 4 carbon atoms.

A is either --R or --Q--COOR',

m and n are positive integers, the sum of m and n being from 10 to 300,and

in which at least two --COOH groups are present.

The second of the two types of polysiloxanes is an amino functionalpolysiloxane which includes one or more hydroxy or alkoxy groupsdirected to silicon (Type II) and having the following composition:##STR2## in which R is a monovalent hydrocarbon group having 1 to 20carbon atoms, preferably an alkyl group having 1 to 7 carbon atoms.

R" is hydrogen or R,

B is --R or --OH or --OR or --TNHCH₂ CH₂ NHR",

C is --OH or --OR,

D is --R, --OH or --OR,

T is a divalent hydrocarbon group having 1 to 8 carbon atoms, preferablyan alkylene group having 1 to 4 carbon atoms,

p, q and r are positive integers, the sum of p, q and r being from 10 to300, and r is at least 2, and

in which preferably at least two primary amino groups are present.

The molar ratio of Type I to Type II polysiloxane in the composition isfrom 1:4 to 9:1. In the case of compositions to be applied to hair, themolar ratio of Type I to Type II is preferably from 1:4 to 1:1; while inthe case of composition to be applied to the skin the molar ratio ispreferably from 1.5:1 to 5:1.

Polymers of the foregoing Type I are available commercially in the formof Q2-7119 (Dow Corning) and Y-7533 (Union Carbide) and can be made byconventional procedures.

Polymers of Type II are also commercially available, such as 478, 531,and Softener CSF, all from Dow Corning; and 1705 from General Electricas well as SWS-756.

The polysiloxanes employed in the present invention are essentiallyinsoluble in water. Dispersing the Type I and Type II polysiloxanesseparately in water or an aqueous medium, or dispersing a mixture of thetwo types in water or an aqueous medium produces a composition which,after drying on hair or skin, cannot be removed by washing withsurface-active agent solution, and thus lacks an essentialcharacteristic of the present invention.

The aqueous dispersions of the present invention are prepared by firstdissolving the Type I and Type II polysiloxanes in the desiredproportions in a volatile organic solvent, preferably one having aboiling point below that of water, then dispersing the solvent solutionin water or aqueous medium. Although applicants do not which to be boundto any particular theory of the mode of operation or functioning of thecomposition, it is believed that the hydroxy or alkoxy groups of theType II polymer condense with each other and that a chemical reactionoccurs between the carboxyl groups of the Type I polysiloxane and theprimary amine groups of the Type II polysiloxane resulting in partialcovalent cross-linking of the two types in the dispersion beforeapplication to the hair or skin, followed by further cross-linking uponformation of a film or coating, thus producing a unique combination ofadvantageous properties in the film or coating.

The dispersions are prepared by first dissolving the Type I and Type IIpolysiloxanes in the desired proportions in a volatile organic solvent,as pointed out above. Among suitable solvents are ethers such as diethylether, di-n-propyl ether, and diisopropyl ether; small hydrocarbons suchas pentane, hexane and benzene; alcohols such as methyl alcohol, ethylalcohol and isopropyl alcohol; ketones such as acetone, methyl ethylketone and the like. The amount of solvent used is not critical;however, it is desired that the solution be sufficiently dilute so as toslow the cross-linking reaction between the two types of silicones whilein solution; in general, the weight of solvent required to dissolve tbhepolysiloxanes is at least as great as the weight of the twopolysiloxanes, but more solvent can be used if desired. It isundesirable to use a large excess of solvent because of the cost anddifficulty of removing it during formation of the desired dispersion.

To the solution of polysiloxanes in an organic solvent may be added anydesired filler, thickener, plasticizer, perfume, sunscreening or insectrepellent agent, conditioner, medicament, moisturizer, wetting agent orsoap, or other active agent for treating hair or skin.

To convert the solution in organic solvent to a dispersion, it is mixedwith water or with an aqueous solution containing additional optionaldesired components or active agents, then subjected to severe mechanicalmixing or shearing stress, for example in a Waring Blender or bysonication. It is also desirable to include the solution in order tofacilitate formation of the dispersion a surfactant or surface activeagent as a dispersing aid and stabilizer. Suitable surfactants includecationic, anionic or amphoteric surface active agents, the non-ionicsurface active agents being preferred. Suitable agents include amongothers sodium lauryl sulfate, sodium dodecyl sulfate, polyoxyethylene(23) lauryl ether, polyoxyethylene stearate, and the like. The amount ofsurface active agent employed may vary depending upon the particularpolysiloxane and particular surface active agent used as well as on theparticle size of the dispersion, and can readily be determined in anyparticular case by simple tests as is well known to those skilled in theart of preparing aqueous dispersion generally. The surface active agentmay be dissolved in the organic solvent solution or it may be dissolvedor dispersed in water, after which the solvent solution and water arethoroughly mixed by mechanical or sonication devices to form an aqueousdispersion and the organic solvent is thereupon removed by evaporation.In order to hasten the removal of solvent, the dispersion may besubjected to reduced pressure and/or heated to its boiling point.Heating tends to accelerate the chemical cross-linking reaction believedto occur between Type I and Type II polysiloxanes.

The relative proportion of total polysiloxane to water or other liquidin the dispersion may vary over a range from about 0.25% to about 30% byweight; for best results the concentration of total polysiloxanes in thedispersion should be from about 1.5% to about 15% by weight. In the caseof a composition to be applied to hair, the total polysiloxanespreferably amount to 1.5 to 5% by weight. The amount of dispersionapplied to the hair may vary widely depending upon individualpreferences, the manner of application, whether by spray or as a lotionor cream rinse or mousse, and the concentration of the polysiloxanes inthe dispersion. If desired, the dispersion may be packaged with aconventional pressure propellent to enable it to be applied as a sprayor aerosol.

When the composition of the present invention is applied to the hair andallowed to remain for as short a time as one minute, it forms a filmadherent to the hair fibers which is not removed by rinsing in water.Heavier and more complete films are formed and deposited on the hairfibers if the composition is allowed to remain on the hair for a longertime before rinsing or if it is heated. Although a water rinse isfrequently desired by the user, it is not essential and the compositionif applied sparingly may simply be allowed to dry on the hair either atroom temperature or at higher temperatures.

The film formed by the composition, with or without a water rinse,supplies desirable characteristics to the hair including a high sheen,good tactile properties and ease of combing even when wet, in additionto set retention when the hair is exposed either to dry conditions or toan atmosphere of high humidity and to repeated combing.

When applied to the skin, the compositions of the present invention"dry" i.e. solidify within as short a time as a minute or less to forman elastic water repellent film or coating which is adherent to the skinand effective in decreasing transepidermal water loss in addition toproviding those special properties supplied by optional added activeagents, as in the case of sunscreens, moisturizers, water proof insectrepellants, medicating and protecting coatings, etc.

The compositions of this invention may be heated at room temperature toabove 100° C. for several minutes to several hours without phaseseparation; nor does separation occur during subsequent cooling to roomtemperature. Such heating, particularly at temperatures above roomtemperature, produces a composition which forms a desirably thicker andmore elastic film when applied to skin than does the composition withoutsuch heating.

The composition of the present invention is further distinguished fromthose of the prior art in its rapid drying or solidyfing time, highdurability in conditions of high humidity or when subjected to waterrinse or combing, and remarkable ease of removal by conventionalshampooing or washing with soap or other effective surface activeagents. In the case of hair treated with the composition of thisinvention, the shampoo preferably contains a small amount of a loweralkyl alcohol or benzyl alcohol, or of a low molecular weightpolyalcohol such as ethylene glycol.

The following specific examples are intended to illustrate more fullythe nature of the invention without acting as a limitation upon itsscope.

EXAMPLE 1

A hair styling and conditioning composition designed to be applied likea cream rinse was prepared as follows:

3.5 g of Down Corning 478 Fluid (a mixture of 50%amino-methoxy-functional dimethylsilicone polymers and 50% isopropanol)and 1.5 g of Down Corning Q2-7119 Fluid (carboxylic acid-functionaldimethylsilicone polymers) were mixed with 20 ml diethylether. Themixture of silicones and ether was mixed with a solution of 0.5 g Myrj53 (PEG 50 stearate) in 44.5 g distilled water and subjected tohigh-shear mixing until a stable white emulsion or dispersion wasproduced. The ether and isopropanol was then removed from this emulsionunder reduced pressure on a rotary evaporator. This emulsion was thencombined with a mixture of 1.5 g Squat 95 (a stearalkonium chloride),1.0 g Brij 52 (Polyoxyethylene(2))cetylether) and 47.5 g distilledwater, which produced a white, creamy, viscous fluid.

The following test demonstrated the humidity-resistant stylingproperties of the foregoing composition versus the properties of a cremerinse (Tame), a styling mousse (Mink Difference Mousse Regular), aliquid styling aid (Mink Difference Liquid Stylizer) and a hair spray(Adorn Extra Hold) all of which are commercially available products.Five-inch long, 1 g tresses of dark brown, virgin hair were employedwith three tresses per product. Each tress was shampooed twice with 0.1ml of White Rain shampoo, then rinsed with 400 ml of water. Any excesswater was squeezed from the tress and the product was applied asdetailed in Table I below.

                  TABLE I                                                         ______________________________________                                        Product     Treatment Procedure                                               ______________________________________                                        Composition Apply 0.5 ml product to damp hair,                                of Example 1                                                                              work through hair. Wait 1 minute. Rinse                                       with 200 ml H.sub.2 O.                                            Tame        Same as above.                                                    Adorn Extra Hold                                                                          Roll hair on 0.5 inch diameter curler                                         immediately after shampooing. Dry at 42° C.                            for 30 minutes and remove curler. Spray                                       hair tress wih product for 5 seconds from a                                   distance of 10 inches.                                            Mink Difference                                                                           Apply 0.4 g product after shampooing.                             Mousse Regular                                                                            without rinsing. Work through hair.                               Mink Difference                                                                           Apply 0.2 ml product after                                        Liquid Stylizer                                                                           shampooing, without rinsing. Work through                                     hair.                                                             ______________________________________                                    

Table II gives the % curl retention of the various products.

The tress was then rolled on a 0.5 inch diameter roller and dried in a42° C. oven for 30 minutes. The tress was allowed to cool to roomtemperature, and then was placed in a 90% relative humidity chamber at70° F. (21° C.) for 30 minutes. The curler was then removed, the tresswas combed through once, and the length of the curled tress wasmeasured. This length was taken as the initial length, Lo. The curl wasagain placed in the relative humidity chamber. The length of the curlwas measured after one and two hours had elapsed, giving the Ltmeasurements. Percent curl retention was calculated using the formulabelow: ##EQU1## L=length of tress fully extended Lo=length of hair attime 0

Lt=length of hair at time t

The results were as shown in Table II:

                  TABLE II                                                        ______________________________________                                        % Curl Retention at 70° C., 90% Relative Humidity                                                     Mink    Mink                                          Compo-            Adorn Difference                                                                            Difference                             Time   sition of         Extra Mousse  Liquid                                 Elapsed                                                                              Example 1 Tame    Hold  Regular Stylize                                ______________________________________                                        1 Hour 79        78      64    69      72                                     2 Hours                                                                              69        55      44    62      62                                     ______________________________________                                    

EXAMPLE 2

The ease of removal of the composition of this invention wasdemonstrated by the following procedure.

Four five-inch long, 1 g tresses of dark brown, virgin hair were used.Tress A was shampooed twice with 0.1 ml of a conventional shampoo (ForOily Hair Only), then was dried in a 42° C. oven for 20 minutes. Thisprocedure was repeated ten times, after which the silicon content of thehair was determined by analysis to be 170 ppm.

Tress B was shampooed twice with 0.1 ml of the same shampoo, and 0.5 mlof the composition described in Example 1 was applied to and workedthrough the tress, and allowed to remain for one minute. The tress wasthen rinsed with 200 ml of water, dried in a 42° C. oven for 20 minutes,and found by analysis to contain 490 ppm silicon.

Tresses C and D were each shampooed twice with 0.1 ml of the sameshampoo as above. Each was then subjected to ten successive repetitionsof the following sequence of steps: treating with 0.5 ml of thecomposition of Example 1 for one minute, rinsing with 200 ml water,drying 20 minutes ina 42° C. oven, and shampooing twice with 0.1 ml ofthe same shampoo as above. Analysis showed the tresses then contained anaverage of 245 ppm of silicon.

The result with Tress A showed the silicon content of the hair nottreated with the composition of Example 1; Tress B showed the siliconcontent after one treatment and no shampooing; and Tresses C and Dshowed successive treatments followed by shampooing each time resultedin no substantial buildup of polysiloxane; i.e. that substantially allof the polysiloxane was removed at each shampooing.

EXAMPLE 3

The following example serves to demonstrate the effectiveness of thisinvention in preventing water loss through human skin.

A composition according to the invention was formed by mixing 7 g DowCorning Q2-7119 (a carboxylic-acid-functional dimethylsilicone), 3 g ofDow Corning 478 (50% isopropanol and 50% amino-methoxy-functionaldimethylsilicone), and 20 ml of diethyl ether. This mixture was slowlyadded to a solution of 1 g sodium lauryl sulfate in 89 g distilledwater. This mixture was subjected to high-shear mixing until a stablewhite emulsion or dispersion was produced. The ether and isopropanolwere removed from the emulsion under reduced pressure on a rotaryevaporator. The resultant emulsion was heated at 100° C. for one hour.This stable, milk white emulsion, when spread on skin, dried rapidly toa clear, imperceptible film, dry to the touch and elastic with the skin.

To measure water loss through the skin, a ServoMed Evaporimeter Epl(ServoMed Co., Sweden) was employed. The pretreatment rate of water losswas measured at a marked area on each forearm of four subjects. Twodrops of the composition described above were spread on one of themarked sites per subject. The emulsion was allowed to dry andequilibrate for an hour. The rate of water loss at the treated site anduntreated site was measured on each subject. The average reduction inthe rate of transepidermal water loss at the treated sites was 23.3%,compared to the rate of water loss at the untreated site. Thisdemonstrates the efficacy of the present invention, the reduction inrate of water loss through the skin being almost twice as great as thatproduced by a conventional commercially available moisturizer under thesame conditions.

What is claimed is:
 1. A composition comprising a solution in a volatileorganic solvent of a mixture comprising two types of polysiloxaneshaving the following average compositions: ##STR3## in which R is amonovalent hydrocarbon group having 1 to 20 carbon atoms,R' is hydrogenor a monovalent hydrocarbon group, Q is a divalent hydrocarbon grouphaving 1 to 8 carbon atoms, A is either --R or --Q--COOR', m and n arepositive integers, the sum of m and n being from 10 to 300, andin whichat least two --COOH groups are present, ##STR4## in which R is amonovalent hydrocarbon group having 1 to 20 carbon atoms, R" is hydrogenor R B is --R or --OH or --OR or --TNHCH₂ CH₂ NHR" C is --OH or --OR Dis --R, --OH or --OR T is a divalent hydrocarbon group having 1 to 8carbon atoms, p, q and r are positive integers, the sum of p, q and rbeing from 10 to 300, and r is at least 2,the molar ratio of Type I toType II being from 1:4 to 9:1.
 2. A composition for application to hairor skin made by dispersing in water a composition as claimed in claim 1followed by removal of said solvent from said dispersion, the amount ofsaid polysiloxanes being from 0.25 to 30% by weight of the dispersion.3. A composition as claimed in claim 1 in which R is an alkyl or benzylgroup having 1 to 7 carbon atoms, R' is an alkyl group having 1 to 4carbon atoms, Q is an alkylene group having 1 to 4 carbon atoms, andinwhich T is an alkylene group having 1 to 4 carbon atoms.
 4. Acomposition for application to hair or skin made by dispersing in watera composition as claimed in claim 3 followed by removal of said solventfrom said dispersion, the amount of said polysiloxanes being from 0.25to 30% by weight of the dispersion.
 5. The method of treating hair toimprove its set-retaining characteristics which comprises applying tothe hair a composition as claimed in claim 2 with or without subsequentrinsing, forming the hair into the desired configuration and allowing itto dry.
 6. The method of treating hair to improve its set-retainingcharacteristics which comprises applying to the hair a composition asclaimed in claim 4 with or without subsequent rinsing, forming the hairinto the desired configuration and allowing it to dry.
 7. The method oftreating human skin to decrease the transepidermal water loss thereofwhich comprises applying thereto a composition as claimed in claim 2 andallowing it to dry.
 8. The method of treating human skin to decrease thetransepidermal water loss thereof which comprises applying thereto acomposition as claimed in claim 4 and allowing it to dry.
 9. The methodof making a composition for application to hair or skin whichcomprisesdissolving in a volatile organic solvent a mixture comprisingtwo types of polysiloxanes having the following average compositions:##STR5## in which R is a monovalent hydrocarbon group having 1 to 20carbon atoms, R' is a hydrogen or a monovalent hydrocarbon group, Q is adivalent hydrocarbon group having 1 to 8 carbon atoms A is either --R or--Q--COOR', m and n are positive integers, the sum of m and n being from10 to 300, and in which at least two --COOH groups are present, ##STR6##in which R is a monovalent hydrocarbon group having 1 to 20 carbonatoms, R" is hydrogen or R B is --R or --OH or --OR or --TNHCH₂ CH₂ NHR"C is --OH or --OR D is --R, --OH or --OR T is a divalent hydrocarbongroup having 1 to 8 carbon atoms, p, q and r are positive integers, thesum of p, q and r being from 10 to 300, and r is at least 2, the molarratio of Type I to Type II being from 1:4 to 9:1, dispersing saidsolution in water, the amount of said polysiloxanes being from 0.25 to30% by weight of the dispersion and removing said solvent from saiddispersion.
 10. The method as claimed in claim 9 in which R is an alkylor benzyl group having 1 to 7 carbon atoms, R' is an alkyl group having1 to 4 carbon atoms, Q is an alkylene group having 1 to 4 carbon atoms,andin which T is an alkylene group having 1 to 4 carbon atoms.
 11. Acomposition comprising an aqueous medium having dispersed therein from0.25 to 30% by weight of a mixture comprising two types of polysiloxaneshaving the following average compositions: ##STR7## in which R is amonovalent hydrocarbon group having 1 to 20 carbon atoms,R' is hydrogenor a monovalent hydrocarbon group, Q is a divalent hydrocarbon grouphaving 1 to 8 carbon atoms, A is either --R or --Q--COOR', m and n arepositive integers, the sum of m and n being from 10 to 300, andin whichat least two --COOH groups are present, ##STR8## in which R is amonovalent hydrocarbon group having 1 to 20 carbon atoms, R" is hydrogenor R B is --R or --OH or --OR or --TNHCH₂ CH₂ NHR" C is --OH or --OR Dis --R, --OH or --OR T is a divalent hydrocarbon group having 1 to 8carbon atoms, p, q and r are positive integers, the sum of p, q and rbeing from 10 to 300, and r is at least 2,the molar ratio of Type I toType II being from 1:4 to 9:1, said dispersion being characterized bythe fact that when applied to hair or skin and dried it can beessentially completely removed by washing with an aqueous solution ofsurface active agent at room temperature.
 12. The method of treatinghair to improve its set-retaining characteristics which comprisesapplying to the hair a composition as claimed in claim 11 with orwithout subsequent rinsing, forming the hair into the desiredconfiguration and allowing it to dry.
 13. The method of treating humanskin to decrease the transepidermal water loss thereof which comprisesapplying thereto a composition as claimed in claim 11 and allowing it todry.